Monodisperse heterotelechelic diol/amine-based polyurethane/urea hybrids for use golf balls

ABSTRACT

A golf ball including a core and a cover layer, where the cover layer includes a curing agent and a polyurethane/urea hybrid prepolymer formed from a polyisocyanate and a monodisperse heterotelechelic polymer having a polydispersity of from about 1.0 to about 1.3, and having the formula:
 
T—Z—Q n —C—Y—W
 
where C is a hydrogenated or unsaturated block derived by anionic polymerization of at least one monomer selected from the group consisting of conjugated dienes, alkenyl-substituted aromatic hydrocarbons, and mixtures thereof; Y and Z are independently branched or straight chain hydrocarbon connecting groups which contains 3–25 carbon atoms optionally substituted with aryl or substituted aryl containing lower alkyl, lower alkylthio, or lower dialkylamino groups; Q is an unsaturated or hydrogenated hydrocarbyl group derived by incorporation of at least one compound selected from the group consisting of conjugated diene hydrocarbons, alkenyl-substituted aromatic hydrocarbons, and mixtures thereof; T and W are different and are selected from either oxygen or nitrogen; and n is an integer from 0 to 5.

FIELD OF THE INVENTION

The invention relates to golf balls and, more particularly, to golfballs having cover(s), cores, and optional intermediate layers, thatinclude monodisperse, hydrophobic, heterotelechelic polyurethane/ureahybrid elastomers.

BACKGROUND OF THE INVENTION

While golf ball construction can vary greatly, most golf balls can beclassified as either solid or wound. Solid golf balls include one-piece,two-piece, and multi-layer constructions. Wound golf balls typicallyinclude a solid, hollow, or fluid-filled center, surrounded by tensionedelastomeric material and a cover. By altering ball construction andcomposition, manufacturers can vary a wide range of playingcharacteristics, such as resilience, durability, spin, and “feel,” eachof which can be optimized for various playing abilities.

By altering ball construction and composition, however, manufacturerscan vary a wide range of characteristics, such as resilience,durability, spin, and “feel,” each of which can be optimized for variousplayer abilities. In particular, the golf ball components that manymanufacturers continually look to improve are the core, intermediatelayers, if present, and covers.

Generally, golf ball cores and/or centers are constructed with apolybutadiene-based polymer composition. The properties of thepolybutadiene composition are controlled by adjusting the cocktail ofperoxides, curing agents, and fillers that are added.

Intermediate and, particularly, cover layers, while conventionallyformed of ionomer-based materials, have, more recently, been formed ofurethane-based materials, each having varying hardness and flexuralmoduli. Polyurethanes have become more preferred, especially for premiumgolf balls, because they have advantageous hardness and resilienceproperties compared to many ionomers. Conventional polyurethanes aretypically formed from a prepolymer including a polyol and an isocyanate,and a curing agent. These polyurethanes, however, are still not idealfor golf ball layers—conventional prepolymer polyols and polyaminestypically have a polydispersity (M_(w)/M_(n), where M_(w) is the WeightAverage Molecular Weight and M_(n) is the Number Average MolecularWeight) of at least 2.0 which can cause decreased impact strength andresiliency.

There remains a need, therefore, for improved polyurethane/urea hybridcompositions, especially those formed from unconventional startingmaterials, such as novel monodisperse (i.e., a polydispersity close to1.0) heterotelechelic polymers (polymers having different functionalgroups on opposing termini, such as primary/secondary amine groups andhydroxyl groups), as well as hydrogenated and/or unprotected analoguesthereof. The monodisperse, hydrophobic heterotelechelic diol/amines, andpolyurethane/urea hybrids resulting therefrom, are suggested for use ina variety of golf ball constructions.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball comprising a corehaving an outer diameter no greater than about 1.62 inches; and a coverlayer comprising a curing agent and a polyurethane/urea hybridprepolymer formed from a polyisocyanate and a monodisperseheterotelechelic polymer having a polydispersity of from about 1.0 toabout 1.3, and having the formula:T—Z—Q_(n)—C—Y—Wwhere C is a hydrogenated or unsaturated block derived by anionicpolymerization of at least one monomer selected from the groupconsisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof; Y and Z are independently branchedor straight chain hydrocarbon connecting groups which contains 3–25carbon atoms optionally substituted with aryl or substituted arylcontaining lower alkyl, lower alkylthio, or lower dialkylamino groups; Qis an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof; T and W are independently,but alternatively, selected from oxygen and nitrogen; and n is aninteger from 0 to 5.

Preferably, the monodisperse heterotelechelic polymer includes

where R═H, alkyl, or aryl and x and y=integer from 1 to 50. In oneembodiment, the core includes a polybutadiene composition and the saltof a halogenated thiophenol, and preferably the salt of a halogenatedthiophenol comprises zinc salt of pentachlorothiophenol.

In another embodiment, the polyisocyanate includes toluene diisocyanate;4,4′-diphenylmethane diisocyanate; polymeric 4,4′-diphenylmethanediisocyanate; carbodiimide-modified 4,4′-diphenylmethane diisocyanate;3,3′-dimethyldiphenyl-4,4′ diisocyanate; naphthalene diisocyanate;p-phenylene diisocyanate; xylene diisocyanate; p-tetramethylxylenediisocyanate; m-tetramethylxylene diisocyanate; ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyldiisocyanate; 1,6-hexamethylene-diisocyanate;dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isophoronediisocyanate; methyl cyclohexylene diisocyanate; triisocyanate of1,6-hexamethylene-diisocyanate; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate; 4,4′-dicyclohexylmethanediisocyanate; or trimethylhexamethylene diisocyanate.

The monodisperse heterotelechelic polymer preferably has apolydispersity of from about 1.0 to about 1.1. In one construction, thecover has a thickness of less than about 0.05 inches and the core has acompression of between about 50 and about 90. In another construction,the core outer diameter is between about 1.54 inches and about 1.62inches. The golf ball is preferably constructed so that it has acoefficient of restitution of greater than about 0.8, more preferablygreater than about 0.81. In an alternative, but preferred construction,the core includes a center and an outer core layer.

The present invention is also directed to a golf ball comprising a core;an intermediate layer; and a cover comprising a curing agent and apolyurethane/urea hybrid prepolymer formed from a polyisocyanate and amonodisperse heterotelechelic polymer having a polydispersity of betweenabout 1.0 and about 1.3, and having the formula:T—Z—Q_(n)—C—Y—Wwhere C is a hydrogenated or unsaturated block derived by anionicpolymerization of at least one monomer selected from the groupconsisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof; Y and Z are independently branchedor straight chain hydrocarbon connecting groups which contains 3–25carbon atoms optionally substituted with aryl or substituted arylcontaining lower alkyl, lower alkylthio, or lower dialkylamino groups; Qis an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof; T and W are independentlyand alternatively selected from oxygen and nitrogen; and n is an integerfrom 0 to 5.

The intermediate layer is preferably an inner cover layer, an outer corelayer, or a water vapor barrier layer. In one embodiment, theintermediate layer is an inner cover layer, and the inner cover layerand the cover each have a thickness of less than about 0.05 inches.Alternatively, the intermediate layer includes the monodisperseheterotelechelic polymer, a monodisperse telechelic polyurethane, or amonodisperse telechelic polyurea. Additionally, the intermediate layermay include ionomers, vinyl resins; polyolefins; polyurethanes;polyureas; polyamides; acrylic resins; thermoplastics; polyphenyleneoxides; thermoplastic polyesters; thermoplastic rubbers; orhighly-neutralized polymers. Most preferably, the monodispersetelechelic polyol has a polydispersity of from about 1.0 to about 1.1.

The present invention is further directed to a golf ball including acore; an intermediate layer; and a cover including a curing agent and apolyurethane prepolymer formed from a polyisocyanate and a monodisperseheterotelechelic polymer having a polydispersity of between about 1.0and about 1.3. Preferably, the intermediate layer is a water vaporbarrier layer having a thickness of from about 0.1 μm to about 75 μm.The monodisperse heterotelechelic polymer most preferably has apolydispersity of between about 1.0 and about 1.1. In one construction,the core has an outer diameter of no greater than about 1.62 inches. Inan alternate construction, the intermediate layer is an inner coverlayer having a hardness of between about 40 and about 75 Shore D; andthe cover is an outer cover layer having a hardness of between about 30and about 60 Shore D. Still further, the inner cover layer may have aflexural modulus of between about 30,000 and about 80,000 psi and thecover has a flexural modulus of between about 10,000 and about 30,000psi.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Broadly, the present invention contemplates a golf ball comprising apolyurethane/urea (or polyurea/urethane) hybrid-type elastomer formedfrom novel monodisperse heterotelechelic polyurethane/urea polymers andhydrogenated and/or unprotected analogues thereof. The golf balls of thepresent invention may be formed from any one of a variety ofconstructions, including a solid, one-piece ball, but preferably includeat least a core and a cover. Cores may be a single core layer or includea center and at least one outer core layer. The innermost portion of thecore, while preferably solid, may alternatively be hollow or a liquid-,gel-, or air-filled sphere. The cover may be a single layer or includemore than one layer, such as a cover formed of an outer cover layer andan inner cover layer. An intermediate or mantle layer may be disposedbetween the core and the cover of the golf ball. The intermediate layer,while typically a solid, contiguous layer, may also be non-contiguouslayer, a vapor barrier layer, or comprise a tensioned elastomeric (ormetal, “hoop stress” type layer) material (i.e., a wound layer).

The monodisperse urethane/urea (or urea/urethane) hybridheterotelechelic polymers of the present invention have a polydispersity(a ratio of M_(w)/M_(n)) of about 1.0 to about 1.3, more preferablyabout 1.0 to about 1.2, and most preferably about 1.0 to about 1.1. As aresult of its monodisperse nature, the heterotelechelic polymers providea more controlled molecular structure which, in turn, results inimproved golf ball performance (i.e., impact strength and resiliency).The monodisperse heterotelechelic polymers of the present invention arenovel and significantly different than conventional heterotelechelicpolymers.

The monodisperse heterotelechelic polyurethaneurea hybrid elastomerssuitable for use in the invention are a product of a reaction between atleast one polyurethane/urea prepolymer and at least one curing agent.The polyurethane/urea prepolymer is a product formed by a reactionbetween at least one polyisocyanate and at least one heterotelechelicpolymer, the heterotelechelic polymer being based on a hydrophobicbackbone, such as hydrocarbons, hydroxy-terminated polybutadienes,polyethers, polycaprolactones, and polyesters. As is well known in theart, a catalyst may be employed to promote the reaction between thecuring agent and the isocyanate and monodisperse heterotelechelicpolyol.

The monodisperse heterotelechelic polyurea/urethane (orpolyurethane/urea) hybrid elastomers suitable for use in the inventionare a product of a reaction between at least one polyurea/urethane (orpolyurethane/urea) prepolymer and at least one curing agent. Thepolyurethane/urea prepolymer is a product formed by a reaction betweenat least one polyisocyanate and at least one monodisperseheterotelechelic polymer (polymer backbone that contains both an amine-and a hydroxy-functional terminus).

The functional monodisperse heterotelechelic (polymers having differentfunctional groups on opposing termini) polydienes and polyolefins of thepresent invention are useful as novel polyurethane/urea prepolymersand/or cross-linkers. The nature of the functional groups on eachterminus, and its protecting group, if present, can also be variedsimply by changing the functionalized initiator or the functionalizingagent. Reactive functionalities include, hydroxyl, carboxyl, secondaryamines, tertiary amines, and derivative functionalities forpolyurethane, polyurea, epoxy, and free radical or radiation curingchemistries, preferably for polyurethane/urea curing chemistry. Polymerswith different functional groups on opposite chain ends, such asprimary/secondary amines on one end and hydroxyl groups on the otherend) allow selective curing chemistries. In addition to linear polymers,radial or star polymer architectures can be produced with functionalgroups on the star arms are possible. The monodisperse heterotelechelicpolymers of the present invention comprise the generic structure:(R₁R₂R₃—A)_(m)—T—Z—Q_(n)—C—Y—W—(B—R₄R₅R₆)_(k)where:

C is a hydrogenated or unsaturated block derived by anionicpolymerization of at least one monomer selected from the groupconsisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof;

Y and Z are independently branched or straight chain hydrocarbonconnecting groups which contains 3–25 carbon atoms optionallysubstituted with aryl or substituted aryl containing lower alkyl, loweralkylthio, or lower dialkylamino groups;

Q is an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof;

T and W are independently selected from oxygen, sulfur, and nitrogen;

(A—R₁R₂R₃)_(m) and (B—R₄R₅R₆)_(k) are each protecting groups in which Aand B are independently selected from Group IVa elements; R₁, R₂, R₃,R₄, R₅, and R₆ are independently defined as hydrogen, alkyl, substitutedalkyl groups containing lower alkyl, lower alkylthio, and lowerdialkylamino groups, aryl or substituted aryl groups containing loweralkyl, lower alkylthio, lower dialkylamino groups, or cycloalkyl andsubstituted cycloalkyl groups containing 5 to 12 carbon atoms; and k andm are 1 when T or W is oxygen or sulfur, and 2 when T or W is nitrogen;and

n is an integer from 0 to 5.

The monomer(s) to be anionically polymerized can be selected from anysuitable monomer capable of anionic polymerization, including conjugatedalkadienes, alkenyl-substituted aromatic hydrocarbons, and mixturesthereof The dienes may be polymerized alone, or in admixture with eachother or with alkenyl-substituted aromatic hydrocarbons to form randomcopolymers, or by charging the dienes to the reaction mixturesequentially, either with each other or with alkenyl-substitutedaromatic hydrocarbons, to form block copolymers. Examples of conjugatedalkadiene hydrocarbons include, but are not limited to, 1,3-butadiene;isoprene; 2,3-dimethyl-1,3-butadiene; 1,3-pentadiene; myrcene;2-methyl-3-ethyl-1,3-butadiene; 2-methyl-3-ethyl-1,3-pentadiene;1,3-hexadiene; 2-methyl-1,3-hexadiene; 1,3-heptadiene;3-methyl-1,3-heptadiene; 1,3-octadiene; 3-butyl-1,3-octadiene;3,4-dimethyl-1,3-hexadiene; 3-n-1,3-pentadiene; 4,5-diethyl- 1,3-octadiene; 2,4-diethyl-1,3 -butadiene; 2,3-di-n-propyl-1,3-butadiene;and 2-methyl-3-isopropyl-1,3-butadiene.

Examples of alkenyl-substituted aromatic hydrocarbons include, but arenot limited to, styrene; α-methylstyrene; vinyltoluene; 2-vinylpyridine;4-vinylpyridine; 1-vinylnaphthalene; 2-vinylnaphthalene;1-α-methylvinylnaphthalene; 2-α-methylvinylnaphathalene;1,2-diphenyl-4-methyl-1-hexene; and mixtures thereof, as well as alkyl,cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof in which thetotal number of carbon atoms in the combined hydrocarbon constituents isgenerally not greater than 18. Examples of these latter compoundsinclude; 3-methylstyrene, 3,5-diethylstyrene; 2-ethyl-4-benzylstyrene;4-phenylstyrene; 4-p-tolylstyrene; 2,4-divinyltoluene; and4,5-dimethyl-1-vinylnaphthalene. U.S. Pat. No. 3,377,404 disclosuresadditional suitable alkenyl substituted aromatic compounds and isincorporated herein, in its entirety, by reference. As used herein, thereference to mixtures of monomers refers to mixtures of conjugateddienes, mixtures of alkenyl-substituted aromatic hydrocarbons, andmixtures of one or more conjugated dienes with one or morealkenyl-substituted aromatic hydrocarbons.

More preferably, the monodisperse heterotelechelic polymers have theformula:T—Z—Q_(n)—C—Y—W

where:

-   -   C is a hydrogenated or unsaturated block derived by anionic        polymerization of at least one monomer selected from the group        consisting of conjugated dienes, alkenyl-substituted aromatic        hydrocarbons, and mixtures thereof;    -   Y and Z are independently branched or straight chain hydrocarbon        connecting groups which contains 3–25 carbon atoms optionally        substituted with aryl or substituted aryl containing lower        alkyl, lower alkylthio, or lower dialkylamino groups;    -   Q is an unsaturated or hydrogenated hydrocarbyl group derived by        incorporation of at least one compound selected from the group        consisting of conjugated diene hydrocarbons, alkenyl-substituted        aromatic hydrocarbons, and mixtures thereof;    -   T and W are independently selected from oxygen and nitrogen, but        are never the same; and    -   n is an integer from 0 to 5.

Examples include, but are not limited to, polymeric hydroxyl/secondaryamines (i.e., poLichelic™-HSA50H), such as those defined by the chemicalstructure 1:

and, additionally, α-hydroxyl-ω-aminepolyethylenebutylene with 50%butylene microstructure (i.e., poLichelic™ CSA-PEB-50);α-Hydroxyl-ω-aminepolybutadiene with 50% vinyl 1,2-microstructure (i.e.,poLichelic™ DH-PBD-50); α-Hydroxyl-ω-carboxylpolyethylenebutylene with50% butylene microstructure (i.e., poLichelic™ HC-PEB-50); andα-Hydroxyl-ω-aminepolyethylenebutylene with 50% butylene microstructure(i.e., poLichelic™ HSA-PEB-50); all of which are commercially availableunder the poLichelic™ tradename from FMC Lithium of Gastonia, N.C.

Suitable diisocyanates which can be used include, without limitation,toluene diisocyanate; 4,4′-diphenylmethane diisocyanate; polymeric4,4′-diphenylmethane diisocyanate; carbodiimide-modified4,4′-diphenylmethane diisocyanate; 3,3′-dimethyldiphenyl-4,4′diisocyanate; naphthalene diisocyanate; p-phenylene diisocyanate; xylenediisocyanate; p-tetramethylxylene diisocyanate; m-tetramethylxylenediisocyanate; ethylene diisocyanate; propylene-1,2-diisocyanate;tetramethylene-1,4-diisocyanate; cyclohexyl diisocyanate;1,6-hexamethylene-diisocyanate; dodecane-1,12-diisocyanate;cyclobutane-1,3 -diisocyanate; cyclohexane-1,3-diisocyanate;cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isophoronediisocyanate; methyl cyclohexylene diisocyanate; triisocyanate of1,6-hexamethylene-diisocyanate; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate; 4,4′-dicyclohexylmethanediisocyanate; trimethylhexamethylene diisocyanate, and mixtures thereof.

Suitable polyols which are appropriate for use in this invention includewithout limitation saturated and unsaturated hydrocarbon polyols;hydroxy-terminated liquid isoprene rubber; hydroxy-terminatedpolybutadiene polyol; polytetramethylene ether glycol (“PTMEG”);poly(oxypropylene) glycol; polyethylene adipate glycol; polyethylenepropylene adipate glycol; polybutylene adipate glycol; diethylene glycolinitiated polycaprolactone; 1,4-butanediol initiated polycaprolactone;1,6-hexanediol initiated polycaprolactone; trimethylol propane initiatedpolycaprolactone; neopentyl glycol initiated polycaprolactone;PTMEG-initiated polycaprolactone and mixtures thereof.

Suitable curatives include without limitation 1,4-butanediol;1,3-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol; propyleneglycol, dipropylene glycol; polypropylene glycol; ethylene glycol;diethylene glycol; polyethylene glycol; resorcinol-di(β-hydroxyethyl)ether and its derivatives; hydroquinone-di(β-hydroxyethyl) ether and itsderivatives; 2-propanol-1,1′-phenylaminobis; tetrahydroxypropyleneethylene diamine; trimethylolpropane;4,4′-methylenebis(2-chloroaniline); 3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 4,4′-methylenebis(2-ethylaniline);4,4′-bis-(sec-butylamino)-diphenylmethane;1,3-bis-(2-hydroxyethoxy)benzene; 1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene; 1,3-bis-{2-[2-hydroxyethoxy) ethoxy]ethoxy}benzene;1,4-bis-(sec-butylamino) benzene; 1,2-bis-(sec-butylamino)benzene;3,5-diethyltoluene-2,4-diamine; 3,5-diethyltoluene-2,6-diamine;tetra-(2-hydroxypropyl)-ethylenediamine; N,N′-dialkyldiamino diphenylmethane; trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylene-bis-(3-chloro-2,6-diethylaniline);1,4-cyclohexyldimethylol; 2-methylpentamethylene-diamine; isomers andmixtures of diaminocyclohexane; isomers and mixtures of cyclohexanebis(methylamine); polytetramethylene ether glycol; isomers and mixturesof cyclohexyldimethylol; triisopropanolamine; diethylene triamine;triethylene tetramine; tetraethylene pentamine; propylene diamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-propylamine; monoethanolamine; diethanolamine;triethanolamine; monoisopropanolamine and diisopropanolamine. The mostpreferred curatives are3,5-dimethylthio-2,4-toluenediamine,3,5-dimethylthio-2,6-toluenediamineand 4,4′-bis-(sec-butylamino)-diphenylmethane.

Suitable catalysts include, but are not limited to bismuth catalyst,oleic acid, triethylenediamine (DABCO®-33LV), di-butyltin dilaurate(DABCO®-T12) and acetic acid. The most preferred catalyst istriethylenediamine (DABCO®-33LV). DABCO® products are sold by AirProducts.

Preferably, the polyurethane elastomers of the present inventioncomprise from about 1 to about 100%, more preferably from about 10 toabout 75% of the cover composition and/or the intermediate layercomposition. About 90 to about 10%, more preferably from about 90 toabout 25% of the cover and/or the intermediate layer composition iscomprised of one or more other polymers and/or other materials asdescribed below. Such polymers include, but are not limited topolyurethane/polyurea ionomers, polyurethanes or polyureas and epoxyresins. Unless otherwise stated herein, all percentages are given inpercent by weight of the total composition of the golf ball layer inquestion.

Other suitable materials which may be combined with the monodisperseheterotelechelic polyurethane/urea hybrid elastomers in forming thecover and/or intermediate layer(s)of the golf balls of the inventioninclude ionic or non-ionic polyurethanes or polyureas, siloxanes andepoxy resins or blends of these materials. For example, the cover and/orintermediate layer may be formed from a blend of at least onemonodisperse heterotelechelic polyurethane/urea elastomer with anionicand cationic urethanes/polyurethanes, urethane epoxies, polyureas andionic polyureas and blends thereof Examples of suitable urethaneionomers are disclosed in U.S. Pat. No. 5,692,974, the disclosure ofwhich is hereby incorporated by reference in its entirety. Otherexamples of suitable polyurethanes are described in U.S. Pat. No.5,334,673. Examples of appropriate polyureas are discussed in U.S. Pat.No. 5,484,870 and examples of suitable polyurethanes cured with epoxygroup containing curing agents are disclosed in U.S. Pat. No. 5,908,358which is incorporated herein, in its entirety, by reference thereto.

A variety of conventional components can be added to the covercompositions of the present invention. These include, but are notlimited to, white pigment such as TiO.sub.2, ZnO, optical brighteners,surfactants, processing aids, density-controlling fillers, UVstabilizers and light stabilizers and foaming agents. Addition of UVabsorbers and light stabilizers to the water resistant polyurethaneelastomers may help to maintain the tensile strength and elongation ofthe polyurethane elastomers. Suitable UV absorbers and light stabilizersinclude TINUVIN® 328, TINUVIN® 213, TINUVIN® 765, TINUVIN® 770 andTINUVIN® 622. The preferred UV absorber is TINUVIN® 328, and thepreferred light stabilizer is TINUVIN® 765. TINUVIN® products areavailable from Ciba-Geigy. Dyes, as well as optical brighteners andfluorescent pigments may also be included in the golf ball coversproduced with polymers formed according to the present invention. Suchadditional ingredients may be added in any amounts that will achievetheir desired purpose.

Other conventional ingredients, e.g., density-controlling fillers,ceramics and glass spheres are well known to the person of ordinaryskill in the art and may be included in cover and intermediate layerblends of the present invention in amounts effective to achieve theirknown purpose.

An optional filler component may be chosen to impart additional densityto blends of the previously described components. The selection of suchfiller(s) is dependent upon the type of golf ball desired (i.e.,one-piece, two-piece multi-component or wound), as will be more fullydetailed below. Generally, the filler will be inorganic, having adensity greater than about 1.5 g/cc, preferably greater than 4 g/cc, andwill be present in amounts between 5 and 65 weight percent based on thetotal weight of the polymer components comprising the layer(s) inquestion. Examples of useful fillers include zinc oxide, barium sulfate,calcium oxide, calcium carbonate and silica, as well as the other wellknown corresponding salts and oxides thereof.

To prevent or minimize the penetration of water vapor into the core ofthe golf ball, a thin water vapor barrier (“WVB”) layer may be disposedanywhere between the core (or center) and the cover, preferablyimmediately around the core. The WVB layer should have a water vaportransmission (“WVT”) rate that is lower than that of the covermaterials, and preferably less than the WVT rate of an ionomer resinsuch as SURLYN®, which is about 0.80 g·mil/100 in²·24 h at 38° C. and90% relative humidity.

In accordance to one embodiment of the invention, the WVB layer is athin polymeric layer that provides a conformal, pinhole-free filmencapsulating the golf ball core. Conformal coatings can offer golf ballcores protection from water vapor absorption, prevent mechanical andthermal damages, resist abrasion, and enhance performance, the moisturevapor barrier layer is a thin and soft rubber layer. Butyl-based ornatural rubbers are also suitable primary ingredients, due to their lowmoisture vapor transmission rates. A preferred metal acrylate is zincdiacrylate. Other suitable primary ingredients include, but are notlimited to, trans-polyisoprene, neoprene, chlorinated polyethylene,balata, acrylics, multi-layer thermoplastic films, blends of ionomers,polyvinyl alcohol copolymer and polyamides, and dispersions of acidsalts of polyetheramines, among others, etc. Additional suitablematerials and methods for forming the WVB layer are disclosed in U.S.application Ser. No. 09/973,342, the disclosure of which is incorporatedherein by reference. The WVB layer is preferably from about 0.1 μm toabout 75 μm thick, more preferably from about 1 μm to about 25 μm thick,most preferably from about 3 μm to about 15 μm thick.

The materials for solid cores include compositions having a base rubber,a crosslinking agent, a filler, and a co-crosslinking or initiatoragent, and preferably, a halogenated thiophenol compound. The baserubber typically includes natural or synthetic rubbers. A preferred baserubber is 1,4-polybutadiene having a cis-structure of at least 40%, morepreferably at least about 90%, and most preferably at least about 95%.Most preferably, the base rubber comprises high-Mooney-viscosity rubber.Preferably, the base rubber has a Mooney viscosity greater than about35, more preferably greater than about 50. Preferably, the polybutadienerubber has a molecular weight greater than about 400,000 and apolydispersity of no greater than about 2.0. Examples of desirablepolybutadiene rubbers include BUNA® CB22 and BUNA® CB23, commerciallyavailable from Bayer of Akron, Ohio; UBEPOL® 360L and UBEPOL® 150L,commercially available from UBE Industries of Tokyo, Japan; andCARIFLEX® BCP820, CARIFLEX® BCP824, and CARIFLEX® 1220, commerciallyavailable from Shell of Houston, Tex. If desired, the polybutadiene canalso be mixed with other elastomers known in the art such as naturalrubber, polyisoprene rubber and/or styrene-butadiene rubber in order tomodify the properties of the core.

The crosslinking agent includes a metal salt, such as a zinc salt or amagnesium unsaturated fatty acid, such as acrylic or methacrylic acid,having 3 to 8 carbon atoms. Examples include, but are not limited to,one or more metal salt diacrylates, dimethacrylates, andmonomethacrylates, wherein the metal is magnesium, calcium, zinc,aluminum, sodium, lithium, or nickel. Preferred acrylates include zincacrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, andmixtures thereof. The crosslinking agent is typically present in anamount greater than about 10 parts per hundred (“pph”) parts of the basepolymer, preferably from about 20 to 40 pph of the base polymer, morepreferably from about 25 to 35 pph of the base polymer. When ahalogenated thiophenol compound is present, in a low cross-linking agentembodiment the agent is present in an amount of less than 25 pph.Alternatively, in a high cross-linking agent embodiment the agent ispresent in an amount of greater than 40 pph.

The initiator agent can be any known polymerization initiator whichdecomposes during the cure cycle. Suitable initiators include organicperoxide compounds, such as dicumyl peroxide; 1,1-di(t-butylperoxy)3,3,5-trimethyl cyclohexane; α,α-bis (t-butylperoxy) diisopropylbenzene;2,5-dimethyl-2,5 di(t-butylperoxy) hexane; di-t-butyl peroxide; andmixtures thereof. Other examples include, but are not limited to, VAROX®231XL and Varox® DCP-R, commercially available from Elf Atochem ofPhiladelphia, Pa.; PERKODOX® BC and PERKODOX® 14, commercially availablefrom Akzo Nobel of Chicago, Ill.; and ELASTOCHEM® DCP-70, commerciallyavailable from Rhein Chemie of Trenton, N.J.

It is well known that peroxides are available in a variety of formshaving different activity. The activity is typically defined by the“active oxygen content.” For example, PERKODOX® BC peroxide is 98%active and has an active oxygen content of 5.80%, whereas PERKODOX®DCP-70 is 70% active and has an active oxygen content of 4.18%. If theperoxide is present in pure form, it is preferably present in an amountof at least about 0.25 pph, more preferably between about 0.35 pph andabout 2.5 pph, and most preferably between about 0.5 pph and about 2pph. Peroxides are also available in concentrate form, which arewell-known to have differing activities, as described above. In thiscase, if concentrate peroxides are employed in the present invention,one skilled in the art would know that the concentrations suitable forpure peroxides are easily adjusted for concentrate peroxides by dividingby the activity. For example, 2 pph of a pure peroxide is equivalent (atthe same percent active oxygen content) to 4 pph of a concentrateperoxide that is 50% active (i.e., 2 divided by 0.5=4).

Halogenated thiophenol compounds are preferably included in the core.Suitable examples of these compounds include, but are not limited to,those having the following general formula:

where R₁–R₅ can be C₁–C₈ alkyl groups; halogen groups; thiol groups(—SH), carboxylated groups; sulfonated groups; and hydrogen; in anyorder (at least on of which is preferably a halogen); and alsopentafluorothiophenol; 2-fluorothiophenol; 3-fluorothiophenol;4-fluorothiophenol; 2,3-fluorothiophenol; 2,4-fluorothiophenol;3,4-fluorothiophenol; 3,5-fluorothiophenol 2,3,4-fluorothiophenol;3,4,5-fluorothiophenol; 2,3,4,5-tetrafluorothiophenol;2,3,5,6-tetrafluorothiophenol; 4-chlorotetrafluorothiophenol;pentachlorothiophenol; 2-chlorothiophenol; 3-chlorothiophenol;4-chlorothiophenol; 2,3-chlorothiophenol; 2,4-chlorothiophenol;3,4-chlorothiophenol; 3,5-chlorothiophenol; 2,3,4-chlorothiophenol;3,4,5-chlorothiophenol; 2,3,4,5-tetrachlorothiophenol;2,3,5,6-tetrachlorothiophenol; pentabromothiophenol; 2-bromothiophenol;3-bromothiophenol; 4-bromothiophenol; 2,3-bromothiophenol;2,4-bromothiophenol; 3,4-bromothiophenol; 3,5-bromothiophenol;2,3,4-bromothiophenol; 3,4,5-bromothiophenol;2,3,4,5-tetrabromothiophenol; 2,3,5,6-tetrabromothiophenol;pentaiodothiophenol; 2-iodothiophenol; 3-iodothiophenol;4-iodothiophenol; 2,3-iodothiophenol; 2,4-iodothiophenol;3,4-iodothiophenol; 3,5-iodothiophenol; 2,3,4-iodothiophenol;3,4,5-iodothiophenol; 2,3,4,5-tetraiodothiophenol;2,3,5,6-tetraiodothiophenoland; and their zinc salts.

Preferably, the halogenated thiophenol compound ispentachlorothiophenol, which is commercially available in neat form orunder the tradename STRUKTOL® A95, a clay-based carrier containing thesulfur compound pentachlorothiophenol loaded at 45 percent (correlatingto 2.4 parts PCTP). STRUKTOL® A95 is commercially available fromStruktol Company of America of Stow, Ohio. PCTP is commerciallyavailable in neat form from eChinachem of San Francisco, Calif. and inthe salt form from eChinachem of San Francisco, Calif. Most preferably,the halogenated thiophenol compound is the zinc salt ofpentachlorothiophenol, which is commercially available from eChinachemof San Francisco, Calif. The halogenated thiophenol compounds (and theirsalts) of the present invention are present in an amount of from about0.5 pph to about 6 pph, preferably between about 0.5 pph and about 1.5pph. In a high halogenated thiophenol compound embodiment, thehalogenated thiophenol is present in an amount greater than about 2 pph,more preferably between about 2.3 pph and about 5 pph, and mostpreferably between about 2.3 and about 4 pph.

Fillers typically include materials such as tungsten, zinc oxide, bariumsulfate, silica, calcium carbonate, zinc carbonate, metals, metal oxidesand salts, regrind (recycled core material typically ground to about 30mesh particle), high-Mooney-viscosity rubber regrind, and the like.Fillers may be added to one or more portions of the golf ball andtypically may include processing aids or compounds to affect Theologicaland mixing properties, density-modifying fillers, fillers to improvetear strength, or reinforcement fillers, and the like. The fillers aregenerally inorganic, and suitable fillers include numerous metals ormetal oxides, such as zinc oxide and tin oxide, as well as bariumsulfate, zinc sulfate, calcium carbonate, barium carbonate, clay,tungsten, tungsten carbide, an array of silicas, and mixtures thereof.Fillers may also include various foaming agents or blowing agents whichmay be readily selected by one of ordinary skill in the art. Fillers mayinclude polymeric, ceramic, metal, and glass microspheres may be solidor hollow, and filled or unfilled. Fillers are typically also added toone or more portions of the golf ball to modify the density thereof toconform to uniform golf ball standards. Fillers may also be used tomodify the weight of the center or at least one additional layer forspecialty balls, e.g., a lower weight ball is preferred for a playerhaving a low swing speed. The invention also includes, if desired, amethod to convert the cis- isomer of the polybutadiene resilient polymercomponent to the trans- isomer during a molding cycle and to form a golfball. A variety of methods and materials suitable for cis-to-transconversion have been disclosed in U.S. Pat. Nos. 6,162,135; 6,465,578;6,291,592; and 6,458,895, each of which are incorporated herein, intheir entirety, by reference thereto.

The materials used in forming either the golf ball center or any portionof the core, in accordance with the invention, may be combined to form amixture by any type of mixing known to one of ordinary skill in the art.Suitable types of mixing include single pass and multi-pass mixing.Suitable mixing equipment is well known to those of ordinary skill inthe art, and such equipment may include a Banbury mixer, a two-rollmill, or a twin screw extruder.

Conventional mixing speeds for combining polymers are typically used.The mixing temperature depends upon the type of polymer components, andmore importantly, on the type of free-radical initiator. Suitable mixingspeeds and temperatures are well-known to those of ordinary skill in theart, or may be readily determined without undue experimentation. Themixture can be subjected to, e.g., a compression or injection moldingprocess, to obtain solid spheres for the center or hemispherical shellsfor forming an intermediate layer. The temperature and duration of themolding cycle are selected based upon reactivity of the mixture. Themolding cycle may have a single step of molding the mixture at a singletemperature for a fixed time duration. The molding cycle may alsoinclude a two-step process, in which the polymer mixture is held in themold at an initial temperature for an initial duration of time, followedby holding at a second, typically higher temperature for a secondduration of time. In a preferred embodiment of the current invention, asingle-step cure cycle is employed. The materials used in forming eitherthe golf ball center or any portion of the core, in accordance with theinvention, may be combined to form a golf ball by an injection moldingprocess, which is also well-known to one of ordinary skill in the art.Although the curing time depends on the various materials selected,those of ordinary skill in the art will be readily able to adjust thecuring time upward or downward based on the particular materials usedand the discussion herein.

Any method known to one of ordinary skill in the art may be used topolyurethanes of the present invention. One commonly employed method,known in the art as a one-shot method, involves concurrent mixing of thepolyisocyanate, polyol, and curing agent. This method results in amixture that is inhomogenous (more random) and affords the manufacturerless control over the molecular structure of the resultant composition.A preferred method of mixing is known as a prepolymer method. In thismethod, the polyisocyanate and the polyol are mixed separately prior toaddition of the curing agent. This method affords a more homogeneousmixture resulting in a more consistent polymer composition. Othermethods suitable for forming the layers of the present invention includereaction injection molding (“RIM”), liquid injection molding (“LIM”),and pre-reacting the components to form an injection moldablethermoplastic polyurethane and then injection molding, all of which areknown to one of ordinary skill in the art.

It has been found by the present invention that the use of a castable,reactive material, which is applied in a fluid form, makes it possibleto obtain very thin outer cover layers on golf balls. Specifically, ithas been found that castable, reactive liquids, which react to form aurethane elastomer material, provide desirable very thin outer coverlayers.

The castable, reactive liquid employed to form the urethane elastomermaterial can be applied over the core using a variety of applicationtechniques such as spraying, dipping, spin coating, or flow coatingmethods which are well known in the art. An example of a suitablecoating technique is that which is disclosed in U.S. Pat. No. 5,733,428,the disclosure of which is hereby incorporated by reference in itsentirety in the present application.

The outer cover is preferably formed around the inner cover by mixingand introducing the material in the mold halves. It is important thatthe viscosity be measured over time, so that the subsequent steps offilling each mold half, introducing the core into one half and closingthe mold can be properly timed for accomplishing centering of the corecover halves fusion and achieving overall uniformity. Suitable viscosityrange of the curing urethane mix for introducing cores into the moldhalves is determined to be approximately between about 2,000 cP andabout 30,000 cP, with the preferred range of about 8,000 cP to about15,000 cP.

To start the cover formation, mixing of the prepolymer and curative isaccomplished in motorized mixer including mixing head by feeding throughlines metered amounts of curative and prepolymer. Top preheated moldhalves are filled and placed in fixture units using centering pinsmoving into holes in each mold. At a later time, a bottom mold half or aseries of bottom mold halves have similar mixture amounts introducedinto the cavity. After the reacting materials have resided in top moldhalves for about 40 to about 80 seconds, a core is lowered at acontrolled speed into the gelling reacting mixture.

A ball cup holds the ball core through reduced pressure (or partialvacuum). Upon location of the coated core in the halves of the moldafter gelling for about 40 to about 80 seconds, the vacuum is releasedallowing core to be released. The mold halves, with core and solidifiedcover half thereon, are removed from the centering fixture unit,inverted and mated with other mold halves which, at an appropriate timeearlier, have had a selected quantity of reacting polyurethaneprepolymer and curing agent introduced therein to commence gelling.Similarly, U.S. Pat. No. 5,006,297 and U.S. Pat. No. 5,334,673 both alsodisclose suitable molding techniques which may be utilized to apply thecastable reactive liquids employed in the present invention. Further,U.S. Pat. Nos. 6,180,040 and 6,180,722 disclose methods of preparingdual core golf balls. The disclosures of these patents are herebyincorporated by reference in their entirety. However, the method of theinvention is not limited to the use of these techniques.

The golf ball layers of the present invention can likewise include oneor more homopolymeric or copolymeric materials, such as:

-   -   (1) Vinyl resins, such as those formed by the polymerization of        vinyl chloride, or by the copolymerization of vinyl chloride        with vinyl acetate, acrylic esters or vinylidene chloride;    -   (2) Polyolefins, such as polyethylene, polypropylene,        polybutylene and copolymers such as ethylene methylacrylate,        ethylene ethylacrylate, ethylene vinyl acetate, ethylene        methacrylic or ethylene acrylic acid or propylene acrylic acid        and copolymers and homopolymers produced using a single-site        catalyst or a metallocene catalyst;    -   (3) Polyurethanes, such as those prepared from polyols and        diisocyanates or polyisocyanates and those disclosed in U.S.        Pat. No. 5,334,673;    -   (4) Polyureas, such as those disclosed in U.S. Pat. No.        5,484,870;    -   (5) Polyamides, such as poly(hexamethylene adipamide) and others        prepared from diamines and dibasic acids, as well as those from        amino acids such as poly(caprolactam), and blends of polyamides        with SURLYN®, polyethylene, ethylene copolymers,        ethyl-propylene-non-conjugated diene terpolymer, and the like;    -   (6) Acrylic resins and blends of these resins with poly vinyl        chloride, elastomers, and the like;    -   (7) Thermoplastics, such as urethanes; olefinic thermoplastic        rubbers, such as blends of polyolefins with        ethylene-propylene-non-conjugated diene terpolymer; block        copolymers of styrene and butadiene, isoprene or        ethylene-butylene rubber; or copoly(ether-amide), such as        PEBAX®, sold by ELF Atochem of Philadelphia, Pa.;    -   (8) Polyphenylene oxide resins or blends of polyphenylene oxide        with high impact polystyrene as sold under the trademark NORYL®        by General Electric Company of Pittsfield, Mass.;    -   (9) Thermoplastic polyesters, such as polyethylene        terephthalate, polybutylene terephthalate, polyethylene        terephthalate/glycol modified and elastomers sold under the        trademarks HYTREL® by E.I. DuPont de Nemours & Co. of        Wilmington, Del., and LOMOD® by General Electric Company of        Pittsfield, Mass.;    -   (10) Blends and alloys, including polycarbonate with        acrylonitrile butadiene styrene, polybutylene terephthalate,        polyethylene terephthalate, styrene maleic anhydride,        polyethylene, elastomers, and the like, and polyvinyl chloride        with acrylonitrile butadiene styrene or ethylene vinyl acetate        or other elastomers; and    -   (11) Blends of thermoplastic rubbers with polyethylene,        propylene, polyacetal, nylon, polyesters, cellulose esters, and        the like.

Any of the cover layers can include polymers, such as ethylene,propylene, butene-1 or hexane-1 based homopolymers or copolymersincluding functional monomers, such as acrylic and methacrylic acid andfully or partially neutralized ionomer resins and their blends, methylacrylate, methyl methacrylate homopolymers and copolymers, imidized,amino group containing polymers, polycarbonate, reinforced polyamides,polyphenylene oxide, high impact polystyrene, polyether ketone,polysulfone, poly(phenylene sulfide), acrylonitrile-butadiene,acrylic-styrene-acrylonitrile, poly(ethylene terephthalate),poly(butylene terephthalate), poly(ethelyne vinyl alcohol),poly(tetrafluoroethylene) and their copolymers including functionalco-monomers, and blends thereof. Suitable cover compositions alsoinclude a polyether or polyester thermoplastic urethane, a thermosetpolyurethane, a low modulus ionomer, such as acid-containing ethylenecopolymer ionomers, including E/X/Y terpolymers where E is ethylene, Xis an acrylate or methacrylate-based softening comonomer present inabout 0 to 50 weight percent and Y is acrylic or methacrylic acidpresent in about 5 to 35 weight percent. Preferably, the acrylic ormethacrylic acid is present in about 8 to 35 weight percent, morepreferably 8 to 25 weight percent, and most preferably 8 to 20 weightpercent.

Any of the inner or outer cover layers and/or cores, centers, and corelayers, may also be formed from polymers containing α,β-unsaturatedcarboxylic acid groups, or the salts thereof, that have been 100 percentneutralized by organic fatty acids. The acid moieties of thehighly-neutralized polymers (“HNP”), typically ethylene-based ionomers,are preferably neutralized greater than about 70%, more preferablygreater than about 90%, and most preferably at least about 100%. TheHNP's can be also be blended with a second polymer component, which, ifcontaining an acid group, may be neutralized in a conventional manner,by the organic fatty acids of the present invention, or both. The secondpolymer component, which may be partially or fully neutralized,preferably comprises ionomeric copolymers and terpolymers, ionomerprecursors, thermoplastics, polyamides, polycarbonates, polyesters,polyurethanes, polyureas, thermoplastic elastomers, polybutadienerubber, balata, metallocene-catalyzed polymers (grafted andnon-grafted), single-site polymers, high-crystalline acid polymers,cationic ionomers, and the like.

The acid copolymers can be described as E/X/Y copolymers where E isethylene, X is an α,β-ethylenically unsaturated carboxylic acid, and Yis a softening comonomer. In a preferred embodiment, X is acrylic ormethacrylic acid and Y is a C₁₋₈ alkyl acrylate or methacrylate ester. Xis preferably present in an amount from about 1 to about 35 weightpercent of the polymer, more preferably from about 5 to about 30 weightpercent of the polymer, and most preferably from about 10 to about 20weight percent of the polymer. Y is preferably present in an amount fromabout 0 to about 50 weight percent of the polymer, more preferably fromabout 5 to about 25 weight percent of the polymer, and most preferablyfrom about 10 to about 20 weight percent of the polymer.

The organic acids are aliphatic, mono-functional (saturated,unsaturated, or multi-unsaturated) organic acids. Salts of these organicacids may also be employed. The salts of organic acids of the presentinvention include the salts of barium, lithium, sodium, zinc, bismuth,chromium, cobalt, copper, potassium, strontium, titanium, tungsten,magnesium, cesium, iron, nickel, silver, aluminum, tin, or calcium,salts of fatty acids, particularly stearic, behenic, erucic, oleic,linoelic or dimerized derivatives thereof. It is preferred that theorganic acids and salts of the present invention be relativelynon-migratory (they do not bloom to the surface of the polymer underambient temperatures) and non-volatile (they do not volatilize attemperatures required for melt-blending).

Thermoplastic polymer components, such as copolyetheresters,copolyesteresters, copolyetheramides, elastomeric polyolefins, styrenediene block copolymers and their hydrogenated derivatives,copolyesteramides, thermoplastic polyurethanes, such ascopolyetherurethanes, copolyesterurethanes, copolyureaurethanes,epoxy-based polyurethanes, polycaprolactone-based polyurethanes,polyureas, and polycarbonate-based polyurethanes fillers, and otheringredients, if included, can be blended in either before, during, orafter the acid moieties are neutralized, thermoplastic polyurethanes.

A variety of conventional components can be added to the covercompositions of the present invention. These include, but are notlimited to, white pigment such as TiO₂, ZnO, optical brighteners,surfactants, processing aids, foaming agents, density-controllingfillers, UV stabilizers and light stabilizers. Saturated polyurethanesare resistant to discoloration. However, they are not immune todeterioration in their mechanical properties upon weathering. Additionof UV absorbers and light stabilizers to any of the above compositionsand, in particular, the polyurethane compositions, help to maintain thetensile strength, elongation, and color stability. Suitable UV absorbersand light stabilizers include TINUVIN® 328, TINUVIN® 213, TINUVIN® 765,TINUVIN® 770 and TINUVIN® 622. The preferred UV absorber is TINUVIN®328, and the preferred light stabilizer is TINUVIN® 765. TINUVIN®products are available from Ciba-Geigy. Dyes, as well as opticalbrighteners and fluorescent pigments may also be included in the golfball covers produced with polymers formed according to the presentinvention. Such additional ingredients may be added in any amounts thatwill achieve their desired purpose.

The resultant golf balls typically have a coefficient of restitution ofgreater than about 0.75, preferably greater than about 0.8, and morepreferably greater than about 0.81. In a non-USGA-conforming embodiment,the golf ball has a COR of greater than about 0.820, preferably greaterthan about 0.830, more preferably greater than about 0.835, and mostpreferably greater than about 0.840. The golf balls of the presentinvention also typically have an Atti compression of less than about120, preferably from about 30 to 90, and more preferably from about 60to 80.

When golf balls are prepared according to the invention, they typicallywill have dimple coverage greater than about 60 percent, preferablygreater than about 65 percent, and more preferably greater than about 75percent. The flexural modulus of the cover on the golf balls, asmeasured by ASTM method D6272-98, Procedure B, is typically greater thanabout 500 psi, and is preferably from about 500 psi to 150,000 psi.

As discussed herein, the outer cover layer is preferably formed from thepolyurethane, polyurea, or hybrid materials of the invention. Inparticular, the material of the outer cover layer should have a materialhardness, as measured by ASTM-D2240, less than about 65 Shore D,preferably less than about 50 Shore D, more preferably between about 25and about 40 Shore D, and most preferably between about 30 and about 40Shore D. The intermediate layer, if present, preferably has a materialhardness of less than about 80 Shore D, more preferably between about 30and about 70 Shore D, and most preferably, between about 50 and about 65Shore D. In a more preferred embodiment, a ratio of the intermediatelayer material hardness to the outer cover layer material hardness isgreater than 1.5.

The cover layer(s) and intermediate layer(s), if present, of theinvention each preferably have a thickness of less than about 0.1inches, more preferably less than about 0.05 inches, and most preferablybetween about 0.02 inches and about 0.04 inches. In a preferredembodiment, the outer cover is formed from the monodisperseheterotelechelic polyurethane/urea hybrid polymers of the presentinvention and has a thickness of from about 0.02 inches to about 0.04inches; and an intermediate layer is present, as an inner cover layer,and has a thickness of from about 0.03 inches to about 0.04 inches. Theintermediate layer in this embodiment may be formed from any of theabove-listed preferred layer materials, including a blend.

It should be understood, especially to one of ordinary skill in the art,that there is a fundamental difference between “material hardness” and“hardness, as measured directly on a golf ball.” Material hardness isdefined by the procedure set forth in ASTM-D2240 and generally involvesmeasuring the hardness of a flat “slab” or “button” formed of thematerial of which the hardness is to be measured. Hardness, whenmeasured directly on a golf ball (or other spherical surface) is acompletely different measurement and, therefore, results in a differenthardness value. This difference results from a number of factorsincluding, but not limited to, ball construction (i.e., core type,number of core and/or cover layers, etc.), ball (or sphere) diameter,and the material composition of adjacent layers. It should also beunderstood that the two measurement techniques are not linearly relatedand, therefore, one hardness value cannot easily be correlated to theother.

In one embodiment, the core (including any optional outer core layers,if present) of the present invention has an Atti compression of betweenabout 50 and about 90, more preferably, between about 60 and about 85,and most preferably, between about 70 and about 85. The overall outerdiameter (“OD”) of the core is no greater than about 1.62 inches,preferably, no greater than 1.60 inches, more preferably between about1.54 inches and about 1.59 inches, and most preferably between about1.56 inches to about 1.58 inches. The OD of the intermediate layer, ifpresent, of the golf balls of the present invention is preferablybetween 1.58 inches and about 1.65 inches, more preferably between about1.59 inches to about 1.63 inches, and most preferably between about 1.60inches to about 1.63 inches.

The present golf ball can have an overall diameter of any size, althoughone preferred diameter of the invention is 1.68 inches because this isthe USGA limit for minimum golf ball diameter. There is no specificationas to the maximum diameter. Golf balls of any size, however, can be usedfor recreational play. The preferred diameter of the present golf ballsis from about 1.60 inches to about 1.800 inches. The more preferreddiameter is from about 1.62 inches to about 1.740 inches. The mostpreferred diameter is about 1.660 inches to about 1.690 inches.

The golf balls of the present invention should have a moment of inertia(“MOI”) of less than about 85 and, preferably, less than about 83. TheMOI is typically measured on model number MOI-005-104 Moment of InertiaInstrument manufactured by Inertia Dynamics of Collinsville, Conn. Theinstrument is plugged into a PC for communication via a COMM port and isdriven by MOI Instrument Software version #1.2.

The polymers of the present invention may also be used in golfequipment, in particular, inserts or coatings for golf clubs (and clubfaces), such as putters, irons, and woods, as well as in golf shoes andcomponents thereof. For example, such inserts can be in the face of agolf club as disclosed in U.S. Pat. No. 5,575,472, which is incorporatedin its entirety by reference herein, or in the back cavity as disclosedin U.S. Pat. No. 5,316,298, which is also incorporated in its entiretyby reference herein.

As used herein, the term “about,” used in connection with one or morenumbers or numerical ranges, should be understood to refer to all suchnumbers, including all numbers in a range.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended solely as illustrations of several aspects of theinvention. Any equivalent embodiments are intended to be within thescope of this invention. Indeed, various modifications of the inventionin addition to those shown and described herein will become apparent tothose skilled in the art from the foregoing description. Suchmodifications are also intended to fall within the scope of the appendedclaims.

1. A golf ball comprising: a core having an outer diameter no greaterthan about 1.62 inches; and a cover layer comprising a curing agent anda polyurethane/urea hybrid prepolymer formed from a polyisocyanate and amonodisperse heterotelechelic polymer having a polydispersity of fromabout 1.0 to about 1.3, and having the formula:T—Z—Q_(n)—C—Y—W where: C is a hydrogenated or unsaturated block derivedby anionic polymerization of at least one monomer selected from thegroup consisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof; Y and Z are independently branchedor straight chain hydrocarbon connecting groups which contains 3–25carbon atoms optionally substituted with aryl or substituted arylcontaining lower alkyl, lower alkylthio, or lower dialkylamino groups; Qis an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof; T and W are different andare selected from either oxygen-containing or nitrogen-containing; and nis an integer from 0 to
 5. 2. The golf ball of claim 1, wherein themonodisperse heterotelechelic polymer comprises

where R═H, alkyl, or aryl and x and y=integer from 1 to
 50. 3. The golfball of claim 1, wherein the core comprises a polybutadiene compositionand the salt of a halogenated thiophenol.
 4. The golf ball of claim 3,wherein the salt of a halogenated thiophenol comprises zinc salt ofpentachlorothiophenol.
 5. The golf ball of claim 1, wherein thepolyisocyanate comprises toluene diisocyanate; 4,4,′-diphenylmethanediisocyanate; polymeric 4,4,′-diphenylmethane diisocyanate;carbodiimide-modified 4,4,′-diphenylmethane diisocyanate;3,3′-dimethyldiphenyl-4,4′diisocyanate; naphthalene diisocyanate;p-phenylene diisocyanate; xylene diisocyanate; p-tetramethylxylenediisocyanate; m-tetramethylxylene diisocyanate; ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyldiisocyanate; 1,6-hexamethylene-diisocyanate;dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; isophoronediisocyanate; methyl cyclohexylene diisocyanate; triisocyanate of1,6-hexamethylene-diisocyanate; triisocyanate of2,2,4-trimethyl-1,6-hexane diisocyanate; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate; 4,4,′-dicyclohexylmethanediisocyanate; or trimethylhexamethylene diisocyanate.
 6. The golf ballof claim 1, wherein the monodisperse heterotelechelic polymer has apolydispersity of from about 1.0 to about 1.1.
 7. The golf ball of claim1, wherein the cover has a thickness of less than about 0.05 inches andthe core has a compression of between about 50 and about
 90. 8. The golfball of claim 1, wherein the core outer diameter is between about 1.54inches and about 1.62 inches.
 9. The golf ball of claim 1, wherein thegolf ball has a coefficient of restitution of greater than about 0.8.10. The golf ball of claim 1, wherein the golf ball has a coefficient ofrestitution of greater than about 0.81.
 11. The golf ball of claim 1,wherein the core comprises a center and an outer core layer.
 12. A golfball comprising: a core; an intermediate layer; and a cover comprising acuring agent and a polyurethane/urea hybrid prepolymer formed from apolyisocyanate and a monodisperse heterotelechelic polymer having apolydispersity of between about 1.0 and about 1.3, and having theformula:T—Z—Q_(n)—C—Y—W where: C is a hydrogenated or unsaturated block derivedby anionic polymerization of at least one monomer selected from thegroup consisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof; Y and Z are independently branchedor straight chain hydrocarbon connecting groups which contains 3–25carbon atoms optionally substituted with aryl or substituted arylcontaining lower alkyl, lower alkylthio, or lower dialkylamino groups; Qis an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof; T and W are different andare selected from either oxygen-containing or nitrogen-containing; and nis an integer from 0 to
 5. 13. The golf ball of claim 12, wherein theintermediate layer is an inner cover layer, an outer core layer, or awater vapor barrier layer.
 14. The golf ball of claim 12, wherein theintermediate layer is an inner cover layer, and the inner cover layerand the cover each have a thickness of less than about 0.05 inches. 15.The golf ball of claim 12, wherein the intermediate layer comprises themonodisperse heterotelechelic polymer, a monodisperse telechelicpolyurethane, or a monodisperse telechelic polyurea.
 16. The golf ballof claim 12, wherein the intermediate layer comprises ionomers, vinylresins; polyolefins; polyurethanes; polyureas; polyamides; acrylicresins; thermoplastics; polyphenylene oxides; thermoplastic polyesters;thermoplastic rubbers; or highly-neutralized polymers.
 17. The golf ballof claim 12, wherein the monodisperse telechelic polyol has apolydispersity of from about 1.0 to about 1.1.
 18. A golf ballcomprising: a core; an intermediate layer; and a cover comprising acuring agent and a polyurethane/urea hybrid prepolymer formed from apolyisocyanate and a monodisperse heterotelechelic polymer having apolydispersity of between about 1.0 and about 1.3 and having theformula:T—Z—Q_(n)—C—Y—W where: C is a hydrogenated or unsaturated block derivedby anionic polymerization of at least one monomer selected from thegroup consisting of conjugated dienes, alkenyl-substituted aromatichydrocarbons, and mixtures thereof: Y and Z are independently branchedor straight chain hydrocarbon connecting groups which contains 3–25carbon atoms optionally substituted with aryl or substituted arylcontaining lower alkyl, lower alkylthio, or lower dialkylamino groups; Qis an unsaturated or hydrogenated hydrocarbyl group derived byincorporation of at least one compound selected from the groupconsisting of conjugated diene hydrocarbons, alkenyl-substitutedaromatic hydrocarbons, and mixtures thereof; T and W are different andare selected from either oxygen-containing or nitrogen-containing; and nis an integer from 0 to
 5. 19. The golf ball of claim 18, wherein theintermediate layer is a water vapor barrier layer having a thickness offrom about 0.1 μm to about 75 μm.
 20. The golf ball of claim 18, whereinthe monodisperse heterotelechelic polymer has a polydispersity ofbetween about 1.0 and about 1.1.
 21. The golf ball of claim 18, whereinthe core has an outer diameter of no greater than about 1.62 inches. 22.The golf ball of claim 18, wherein the intermediate layer is an innercover layer having a hardness of between about 40 and about 75 Shore D;and the cover is an outer cover layer having a hardness of between about30 and about 60 Shore D.
 23. The golf ball of claim 22, wherein theinner cover layer has a flexural modulus of between about 30,000 andabout 80,000 psi and the cover has a flexural modulus of between about10,000 and about 30,000 psi.